CN111632622A - Preparation method and application of carbon nano tube metal symbiotic material - Google Patents

Preparation method and application of carbon nano tube metal symbiotic material Download PDF

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CN111632622A
CN111632622A CN202010660318.8A CN202010660318A CN111632622A CN 111632622 A CN111632622 A CN 111632622A CN 202010660318 A CN202010660318 A CN 202010660318A CN 111632622 A CN111632622 A CN 111632622A
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nano tube
carbon nano
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张伟
刘俊霞
张磊
班渺寒
张新庄
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Shaanxi Yanchang Petroleum Group Co Ltd
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
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    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

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Abstract

The invention discloses a preparation method of a carbon nano tube metal symbiotic material, which comprises the following steps: (1) mixing a metal source and a carrier, adding the mixture into deionized water, soaking for 1h under ultrasonic treatment, filtering, washing obtained filter residue with the deionized water, drying and calcining to obtain a metal-based catalyst; (2) placing metal-based catalyst in a reactor, introducing nitrogen to replace air, introducing methane for 0.5h, heating to 700 deg.C, introducing methane, reacting for 1-3h, and introducing methane againReducing the temperature of the nitrogen to room temperature in the nitrogen atmosphere to obtain the carbon nano tube metal intergrowth material; wherein the metal source is a mixture of a cobalt source and a manganese source; meanwhile, the invention discloses the application of the carbon nano tube metal symbiotic material in catalyzing Fischer-Tropsch synthesis reaction. The carbon nano tube metal symbiotic material prepared by the invention is directly used for catalyzing Fischer-Tropsch synthesis, metal is not easy to run off, the service life is long, the reaction activity is good, and C4‑C20The product selectivity is high.

Description

Preparation method and application of carbon nano tube metal symbiotic material
Technical Field
The invention belongs to the technical field of carbon nanotubes, and particularly relates to a preparation method and application of a carbon nanotube metal intergrowth material.
Background
The cobalt-based catalyst can catalyze the Fischer-Tropsch synthesis reaction at a lower reaction temperature, has high hydrogenation activity and higher carbon chain growth capability, and is considered as the Fischer-Tropsch synthesis reaction catalyst with the greatest development prospect. Because cobalt is relatively expensive compared to iron and cobalt resources are limited, increasing catalyst activity and improving product selectivity while reducing the amount of cobalt metal is a major concern. Cobalt is the active metal in catalyzing fischer-tropsch synthesis, and cobalt based fischer-tropsch catalysts currently under investigation are typically supported.
The carrier is an important component of the catalyst, and the type and the property of the carrier have great influence on the activity, the service life and the selectivity of the catalyst. The influence of the carrier on the activity of the catalyst and the selectivity of the product of the Fischer-Tropsch reaction is very complicated, and the structural performance of the catalyst is closely related to the specific surface, acidity, pore structure and the like of the carrier. A commonly used support for Fischer-Tropsch cobalt-based catalysts is SiO2，Al2O3，TiO2Molecular sieves and carbon materials, and the like. SiO 22Has large specific surface area, strong acid resistance, wear resistance and heat resistance and is widely used as a carrier of a Fischer-Tropsch synthesis catalyst, but SiO2When used as a carrier, the cobalt catalyst undergoes a surface reaction with the cobalt metal when the cobalt metal has a high degree of dispersion and small particles, and forms a compound that is difficult to reduce, resulting in a decrease in the fischer-tropsch activity of the cobalt-based catalyst. Al (Al)2O3Has a small specific surface area, cobalt in Al2O3The dispersibility on the support is inferior to that on SiO2Good on the carrier, when the roasting temperature is higher, cobalt and Al2O3Strong interaction can occur, spinel compounds which are difficult to reduce are generated, and the activity of the catalyst and the selectivity of liquid hydrocarbon are obviously reduced. TiO 22The catalyst as carrier has high-temperature reducibilityGood, high low-temperature activity, etc., but TiO2The carrier is smaller than the surface, and an auxiliary agent is required to be added to adjust the pore structure. When the traditional oxide is used as a cobalt-based catalyst carrier, strong interaction exists between the carrier and cobalt, mixed oxide which is difficult to reduce and has no reaction activity is generated in the reaction, and the cobalt metal is agglomerated due to high-temperature reduction, so that the utilization rate of the active metal is reduced, and the reduction of the catalyst cost and the improvement of the Fischer-Tropsch reaction activity are not facilitated.
The carbon material comprises activated carbon, carbon nanofiber, carbon nanotube and the like, and is an excellent catalyst carrier with large specific surface area, high thermal stability and strong adsorption capacity and dispersion capacity. Because the surface is inert and does not interact with active components, the activated carbon is the carbon material carrier which is most widely applied at present, and the activated carbon-loaded cobalt-based catalyst is also used for researching the catalytic Fischer-Tropsch reaction, but because the natural carbon source for producing the activated carbon contains impurities such as heavy metal, sulfur and the like, the impurities such as the heavy metal, the sulfur and the like in the activated carbon as the carrier need to be removed in advance, and the removal process is complicated, the conditions are harsh and the cost is high. The carbon nano tube as a novel nano material has high structural regularity, high mechanical strength, strong stability and good structural stability under high temperature and high pressure conditions, and can avoid introducing impurities such as heavy metal, sulfur and the like into a carbon source in the synthesis stage, so that in recent years, the research on the carbon nano tube as a cobalt Fischer-Tropsch synthesis catalyst carrier is more and more. However, the conventional carbon nanotube supported catalyst requires separation and purification of the synthesized carbon nanotube carrier, and has a complicated process, a large operation cost, and a low yield of carbon nanotubes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the carbon nano tube metal symbiotic material, the preparation method is simple, and compared with a supported catalyst, the prepared carbon nano tube metal symbiotic material has the advantages that the active metal is not easy to lose, and the service life is long; meanwhile, the invention also provides the application of the carbon nano tube metal symbiotic material in catalytic Fischer-Tropsch synthesis, when the carbon nano tube metal symbiotic material is used for catalytic Fischer-Tropsch synthesis, the reaction activity is high, and C is4-C20The selectivity of the product is high.
A preparation method of a carbon nano tube metal symbiotic material comprises the following steps:
(1) mixing a metal source and a carrier, adding the mixture into deionized water, soaking for 1h under ultrasonic treatment, filtering, washing obtained filter residue with the deionized water, drying and calcining to obtain a metal-based catalyst;
(2) placing a metal-based catalyst in a reactor, firstly introducing nitrogen to replace air, then introducing methane for 0.5h, heating to 700 ℃, continuing introducing methane, reacting for 1-3h, introducing nitrogen again, and reducing the temperature to room temperature in the nitrogen atmosphere to obtain the carbon nano tube metal symbiotic material;
wherein the metal source is a cobalt source and a manganese source according to the molar ratio of cobalt to manganese of (5-10): 1, mixing;
in the metal-based catalyst, the content of metal accounts for 30-80% of the mass of the metal-based catalyst based on the mass of the corresponding metal oxide.
Preferably, the metal source is a nitrate of the corresponding metal.
Preferably, the calcination temperature in the step (1) is 400-500 ℃, and the calcination time is 4-5 h.
Preferably, the space velocity of the methane is 10000-.
Preferably, the carrier is a small crystal grain ZSM-5 molecular sieve with the grain diameter of 300 nm.
The application of the carbon nano tube metal symbiotic material specifically comprises the following steps: the carbon nano tube metal intergrowth material is used for catalyzing Fischer-Tropsch synthesis reaction, and is obtained by the preparation method.
Preferably, the catalytic fischer-tropsch synthesis reaction is specified as follows: placing the carbon nano tube metal symbiotic material in a fixed bed reactor, introducing hydrogen, reducing for 12h at 400 ℃ under normal pressure, cooling to 180 ℃, stopping introducing the hydrogen, switching to synthesis gas, and continuously reacting for 10h at 220 ℃ under 2.0 MPa; the synthesis gas is H with the volume ratio of 2:12And CO, the volume space velocity of the synthetic gas is 1000h-1。
The small crystal grain ZSM-5 molecular sieve with the grain diameter of 300nm is prepared by adopting the prior art.
The invention has the advantages that:
the method takes cobalt and manganese as metal sources, grows the carbon nano tubes on the metal particles, synthesizes the carbon nano tube metal intergrowth material in situ, has simple preparation process, directly uses the carbon nano tube metal intergrowth material synthesized in situ for catalyzing Fischer-Tropsch synthesis, has the advantages of difficult metal loss in the catalysis Fischer-Tropsch synthesis reaction, long service life, good reaction activity and C4-C20The product selectivity is high.
Detailed Description
Example 1
A preparation method of a carbon nano tube metal symbiotic material comprises the following steps:
(1) 29.1g of Co (NO)3)2·6H2O、5.02g Mn(NO3)2·4H2Mixing O and 21.53g of a small-crystal-grain ZSM-5 molecular sieve carrier with the particle size of 300nm, adding the mixture into deionized water, soaking for 1 hour under ultrasonic treatment, filtering, washing obtained filter residue with the deionized water, drying, and calcining for 5 hours at 420 ℃ to obtain a metal-based catalyst; wherein, the molar ratio of cobalt to manganese is 5, and the content of cobalt and manganese in the metal-based catalyst accounts for 30% of the mass of the metal-based catalyst by the mass of corresponding oxides;
(2) and placing the metal-based catalyst in a reactor, firstly introducing nitrogen to replace air, then introducing methane for 0.5h, wherein the space velocity of the methane is 20000mL/g/h, heating to 700 ℃, continuing to introduce the methane, controlling the space velocity of the methane to be 10000mL/g/h, reacting for 2h, introducing nitrogen again, and reducing the temperature to room temperature in the nitrogen atmosphere to obtain the carbon nano tube metal intergrowth material.
Example 2
A preparation method of a carbon nano tube metal symbiotic material comprises the following steps:
(1) 29.1g of Co (NO)3)2·6H2O、3.35g Mn(NO3)2·4H2Mixing O and 10.57g of small crystal grain ZSM-5 molecular sieve carrier with the grain diameter of 300nm, adding the mixture into deionized water, soaking for 1 hour under ultrasonic treatment, filtering, and using the obtained filter residue to remove the deionized waterWashing with water, drying, and calcining at 500 ℃ for 4h to obtain a metal-based catalyst; wherein the molar ratio of cobalt to manganese is 7.5:1, and the content of cobalt and manganese in the metal-based catalyst accounts for 45% of the mass of the metal-based catalyst by the mass of corresponding oxides;
(2) placing the metal-based catalyst in a reactor, firstly introducing nitrogen to replace air, then introducing methane for 0.5h, wherein the space velocity of the methane is 10000mL/g/h, heating to 700 ℃, continuing to introduce the methane, controlling the space velocity of the methane to be 10000mL/g/h, reacting for 1.5h, introducing nitrogen again, and reducing the temperature to room temperature in the nitrogen atmosphere to obtain the carbon nano tube metal intergrowth material.
Example 3
A preparation method of a carbon nano tube metal symbiotic material comprises the following steps:
(1) 29.1g of Co (NO)3)2·6H2O、2.51g Mn(NO3)2·4H2Mixing O and 2.09g of a small-crystal-grain ZSM-5 molecular sieve carrier with the particle size of 300nm, adding the mixture into deionized water, soaking for 1 hour under ultrasonic treatment, filtering, washing obtained filter residue with the deionized water, drying, and calcining for 5 hours at 450 ℃ to obtain a metal-based catalyst; wherein the molar ratio of cobalt to manganese is 10:1, and the content of cobalt and manganese in the metal-based catalyst accounts for 80% of the mass of the metal-based catalyst by the mass of corresponding oxides;
(2) and placing the metal-based catalyst in a reactor, firstly introducing nitrogen to replace air, then introducing methane for 0.5h, heating to 700 ℃, continuing to introduce methane, controlling the methane space velocity at 15000 mL/g/h, reacting for 3h, introducing nitrogen again, and reducing the temperature to room temperature in the nitrogen atmosphere to obtain the carbon nano tube metal intergrowth material.
Example 4
A preparation method of a carbon nano tube metal symbiotic material comprises the following steps:
(1) 29.1g of Co (NO)3)2·6H2O、2.79g Mn(NO3)2·4H2O and 6.92g of small crystal grain ZSM-5 molecular sieve carrier with the grain diameter of 300nm are mixed and addedSoaking in deionized water for 1h under ultrasonic treatment, filtering, washing the obtained filter residue with deionized water, drying, and calcining at 450 ℃ for 4h to obtain a metal-based catalyst; wherein the molar ratio of cobalt to manganese is 9:1, and the content of cobalt and manganese in the metal-based catalyst accounts for 55% of the mass of the metal-based catalyst by the mass of corresponding oxides;
(2) and placing the metal-based catalyst in a reactor, firstly introducing nitrogen to replace air, then introducing methane for 0.5h, wherein the space velocity of the methane is 10000mL/g/h, heating to 700 ℃, continuing to introduce the methane, controlling the space velocity of the methane to be 20000mL/g/h, reacting for 2h, introducing nitrogen again, and reducing the temperature to room temperature in the nitrogen atmosphere to obtain the carbon nano tube metal intergrowth material.
Example 5
A preparation method of a carbon nano tube metal symbiotic material comprises the following steps:
(1) 29.1g of Co (NO)3)2·6H2O、4.18g Mn(NO3)2·4H2Mixing O and 3.83g of a small-crystal-grain ZSM-5 molecular sieve carrier with the particle size of 300nm, adding the mixture into deionized water, soaking for 1 hour under ultrasonic treatment, filtering, washing obtained filter residue with the deionized water, drying, and calcining for 5 hours at 400 ℃ to obtain a metal-based catalyst; wherein the molar ratio of cobalt to manganese is 6:1, and the content of cobalt and manganese in the metal-based catalyst accounts for 70% of the mass of the metal-based catalyst by the mass of corresponding oxides;
(2) placing the metal-based catalyst in a reactor, firstly introducing nitrogen to replace air, then introducing methane for 0.5h, wherein the space velocity of the methane is 10000mL/g/h, heating to 700 ℃, continuing to introduce the methane, controlling the space velocity of the methane to be 10000mL/g/h, reacting for 2.5h, introducing nitrogen again, and reducing the temperature to room temperature in the nitrogen atmosphere to obtain the carbon nano tube metal intergrowth material.
Example 6
The application comprises the following steps:
the carbon nanotube metal intergrowth materials prepared in examples 1 to 5 were used to catalyze the fischer-tropsch synthesis reaction, as follows:
weighing 1g of carbon nanotubesPutting the metal symbiotic material in a fixed bed reactor, introducing hydrogen, reducing at 400 ℃ for 12H under normal pressure, cooling to 180 ℃, stopping introducing the hydrogen, and switching to synthesis gas (H)2The volume ratio of/CO is 2: 1), and the volume space velocity of the synthetic gas is 1000h-1Continuously reacting for 10h at 2.0MPa and 220 ℃, analyzing a reaction product by online gas chromatography, detecting a hydrocarbon product by an FID (flame ionization detector) and detecting a gas product by a TCD (thermal conductivity detector); the reaction results of the carbon nanotube metal intergrowth materials prepared in examples 1 to 5 when used for catalyzing the fischer-tropsch synthesis reaction are shown in table 1;
TABLE 1 results of reactions of the carbon nanotube metal intergrowth materials prepared in examples 1 to 5 in the catalysis of Fischer-Tropsch synthesis reaction
Figure DEST_PATH_IMAGE001
；
Adopting the carbon nano tube metal symbiotic material prepared in the embodiment 5, continuously reacting for 10 hours at 220 ℃ under the reaction condition of the step (I) for respectively prolonging the reaction time to different reaction times of 20 hours, 60 hours, 100 hours, 150 hours, 200 hours and 300 hours, wherein the reaction results are shown in a table 2;
TABLE 2 results of the reactions at different reaction times
Figure 888836DEST_PATH_IMAGE002
As can be seen from the data in the table, the carbon nano tube metal symbiotic material synthesized by the method is used for catalyzing Fischer-Tropsch synthesis reaction, and the CO conversion rate and C are increased along with the prolonging of the reaction time4-C20The product selectivity is not obviously reduced, which shows that the carbon nano tube metal symbiotic material is not easy to lose active metal when used for catalyzing the Fischer-Tropsch synthesis reaction catalyst, has good stability and long service life of the catalyst, and has good industrial application prospect.

Claims (7)

1. A preparation method of a carbon nano tube metal symbiotic material is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing a metal source and a carrier, adding the mixture into deionized water, soaking for 1h under ultrasonic treatment, filtering, washing obtained filter residue with the deionized water, drying and calcining to obtain a metal-based catalyst;
(2) placing a metal-based catalyst in a reactor, firstly introducing nitrogen to replace air, then introducing methane for 0.5h, heating to 700 ℃, continuing introducing methane, reacting for 1-3h, introducing nitrogen again, and reducing the temperature to room temperature in the nitrogen atmosphere to obtain the carbon nano tube metal symbiotic material;
wherein the metal source is a cobalt source and a manganese source according to the molar ratio of cobalt to manganese of (5-10): 1, mixing;
in the metal-based catalyst, the content of metal accounts for 30-80% of the mass of the metal-based catalyst based on the mass of the corresponding metal oxide.
2. The method for preparing a carbon nanotube-metal intergrowth material according to claim 1, characterized in that: the metal source is a nitrate of the corresponding metal.
3. The method for preparing a carbon nanotube-metal intergrowth material according to claim 1, characterized in that: the calcining temperature in the step (1) is 400-500 ℃, and the calcining time is 4-5 h.
4. The method for preparing a carbon nanotube-metal intergrowth material according to claim 1, characterized in that: the space velocity of the methane is 10000-.
5. The method for preparing a carbon nanotube-metal intergrowth material according to claim 1, characterized in that: the carrier is a small crystal grain ZSM-5 molecular sieve with the grain diameter of 300 nm.
6. The application of the carbon nano tube metal intergrowth material is characterized in that: the carbon nano tube metal intergrowth material is used for catalyzing Fischer-Tropsch synthesis reaction, and is obtained by the preparation method of any one of claims 1 to 5.
7. According to the rightThe application of the carbon nanotube metal intergrowth material according to claim 6 is characterized in that: the catalytic Fischer-Tropsch synthesis reaction is as follows: placing the carbon nano tube metal symbiotic material in a fixed bed reactor, introducing hydrogen, reducing for 12h at 400 ℃ under normal pressure, cooling to 180 ℃, stopping introducing the hydrogen, switching to synthesis gas, and continuously reacting for 10h at 220 ℃ under 2.0 MPa; the synthesis gas is H with the volume ratio of 2:12And CO, the volume space velocity of the synthetic gas is 1000h-1。
CN202010660318.8A 2020-07-10 2020-07-10 Preparation method and application of carbon nano tube metal symbiotic material Pending CN111632622A (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN115582126A (en) * 2022-09-22 2023-01-10 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) Efficient chlorine poisoning resistant flue gas ozonolysis catalyst and preparation method and application thereof
CN117142459A (en) * 2023-09-01 2023-12-01 南通大学 Three-dimensional carbon nanotube material and preparation method and application thereof

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